CN109651544A - Hydrophobic nano-silica modified polyacrylate dispersion liquid and preparation method thereof - Google Patents
Hydrophobic nano-silica modified polyacrylate dispersion liquid and preparation method thereof Download PDFInfo
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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Abstract
A kind of hydrophobic nano-silica modified polyacrylate dispersion liquid and preparation method thereof, hydrophobic nano-silica modified polyacrylate dispersion liquid includes each component of following mass parts: 40 parts to 66.7 parts of hydrophobic nano-silica；10 parts to 15 parts of surfactant；243 parts to 264 parts of water；The hydrophobic nano-silica modified polyacrylate dispersion liquid further includes at least one of the monomer of following mass parts: 80 parts to 100 parts of fluorine-containing alkyl acrylate monomer；15 parts to 100 parts of long chain hydrocarbon groups acrylate monomer.Above-mentioned dispersion liquid, polymer polyacrylate can include tool at least one of fluorohydrocarbon base acrylate monomer and long chain hydrocarbon groups acrylate monomer monomeric building blocks, fluorine-containing alkyl or long chain hydrocarbon groups in polymer polyacrylate can assign polymer preferable waterproofness, and it is good to process duration.Also there is preferable washing fastness when applied to textile.
Description
Technical field
The present invention relates to water-proofing treatment technical fields, more particularly to a kind of hydrophobic nano-silica modified polypropene
Acid esters dispersion liquid and preparation method thereof.
Background technique
Acrylate polymer has certain waterproof performance, especially fluorinated acrylate polymer or propylene containing long-chain
Acid ester polymer waterproofness more preferably, is commonly used for water-proofing treatment technical field.
However, in order to reduce production cost, waterproof acrylate polymer applies factory with the raising of human cost
Family wishes that above-mentioned polymer has preferable processing duration, i.e., same acrylate polymer can carry out more surfaces
Water-proofing treatment, it can greater number of substrate sample is handled, so how to improve the processing duration of acrylate polymer
Hot issue as field concern.In addition, washing fastness is also emphasis when above-mentioned acrylate polymer is used for textile
The index of concern.
Summary of the invention
Based on this, it is necessary to provide it is a kind of can be improved processing duration and can be improved the hydrophobicity of washing fastness receive
Silica modified polyacrylate dispersion liquid of rice and preparation method thereof.
A kind of hydrophobic nano-silica modified polyacrylate dispersion liquid, each component including following mass parts:
40 parts to 66.7 parts of hydrophobic nano-silica；
10 parts to 15 parts of surfactant；
243 parts to 264 parts of water；
The hydrophobic nano-silica modified polyacrylate dispersion liquid further includes in the monomer of following mass parts
It is at least one:
80 parts to 100 parts of fluorine-containing alkyl acrylate monomer；
15 parts to 100 parts of long chain hydrocarbon groups acrylate monomer.
The molecular formula of the fluorine-containing alkyl acrylate monomer is CH in one of the embodiments,2=CR1COOR2,
Middle R1For H, Cl or C1~4Linear paraffin, R2For C4~16Fluorine-containing alkyl.
The fluorine-containing alkyl acrylate monomer is perfluoro hexyl ethyl propylene acid esters in one of the embodiments,.
The long chain hydrocarbon groups acrylate monomer is CH in one of the embodiments,2=CR3COOR4It indicates, wherein R3
For H or C1~4Linear paraffin, R4For C12~30Alkyl.
The long chain hydrocarbon groups acrylate monomer is octadecyl acrylate in one of the embodiments,.
The quality of the dewatering nano silica is no more than the hydrophobic nano dioxy in one of the embodiments,
The 20% of SiClx modified polyacrylate dispersion liquid gross mass.
The hydrophobic nano-silica passes through nano silicon dioxide sol and alkyl silicon in one of the embodiments,
Siloxane compound or alkyl siloxane polymer reaction are prepared,
The alkylsiloxane compound includes the silicone compounds with hydrophobic grouping, the alkylsiloxane polymerization
Object includes the siloxane polymer with hydrophobic grouping.
The silicone compounds containing hydrophobic grouping are selected from isobutyl group tri-alkoxy silicon in one of the embodiments,
Alkane, butyl trialkoxy silane, octyltrialkoxysilane, dodecyl trialkoxy silane, cetyl tri-alkoxy silicon
One of alkane and octadecyltrialkoxysilane, the siloxane polymer containing hydrophobic grouping are methyl alkoxy silicon
Oil.
The silicone compounds containing hydrophobic grouping or polymer are isobutyl group front three in one of the embodiments,
At least one of oxysilane, octyl trimethoxy silane and MethylethoxylsiliconFluid Fluid.
A kind of system of hydrophobic nano-silica modified polyacrylate dispersion liquid described in any embodiment as above
Preparation Method includes the following steps: in one of the embodiments,
Reaction kettle is added in each component, 40~45 DEG C of progress pre-emulsifications is warming up to, obtains emulsion；
By emulsion high-pressure homogeneous 30 minutes under the pressure of 400bar-500bar, homogenizing fluid is obtained；
Initiator is added into homogenizing fluid, after stirring and evenly mixing, is warming up to 70~75 DEG C of reaction 5h, that is, described dredge is prepared
Water-based nano silicon dioxide modified polyacrylate dispersion liquid.
Above-mentioned hydrophobic nano-silica modified polyacrylate dispersion liquid, hydrophobic nano-silica and hydrofluorocarbons
Base acrylate monomer or long chain hydrocarbon groups acrylate monomer polymerize the polyacrylate of acquisition, polymer poly after emulsifying altogether
Acrylate can include tool at least one of fluorohydrocarbon base acrylate monomer and long chain hydrocarbon groups acrylate monomer monomer knot
Structure unit, fluorine-containing alkyl or long chain hydrocarbon groups in polymer polyacrylate can assign polymer preferable waterproofness, can
To form microcosmic concaveconvex structure in substrate surface, waterproof performance and durable water resistant performance are further improved, and process and continue
Property is good.When above-mentioned hydrophobic nano-silica modified polyacrylate dispersion liquid is applied to textile, it may have preferable resistance to
Wash performance.
Specific embodiment
To facilitate the understanding of the present invention, in order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, under
Specific embodiments of the present invention will be described in detail in face.Many details are explained in the following description in order to fill
The sub-argument solution present invention, gives better embodiment of the invention.But the present invention can come in many different forms in fact
It is existing, however it is not limited to embodiments described herein.On the contrary, the purpose of providing these embodiments is that making to public affairs of the invention
Open the more thorough and comprehensive of content understanding.The invention can be embodied in many other ways as described herein, ability
Field technique personnel can do similar improvement without violating the connotation of the present invention, therefore the present invention is not by following public tool
The limitation of body embodiment.Unless otherwise defined, all technical and scientific terms used herein and belong to skill of the invention
The normally understood meaning of the technical staff in art field is identical.Term used herein is intended merely to describe specific embodiment party
The purpose of formula, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more relevant listed
Any and all combinations of project.
In one embodiment, a kind of hydrophobic nano-silica modified polyacrylate dispersion liquid, including following mass parts
Each component:
40 parts to 66.7 parts of hydrophobic nano-silica；
10 parts to 15 parts of surfactant；
243 parts to 264 parts of water；
The hydrophobic nano-silica modified polyacrylate dispersion liquid further includes in the monomer of following mass parts
It is at least one:
80 parts to 100 parts of fluorine-containing alkyl acrylate monomer；
15 parts to 100 parts of long chain hydrocarbon groups acrylate monomer.
Above-mentioned hydrophobic nano-silica modified polyacrylate dispersion liquid, hydrophobic nano-silica and hydrofluorocarbons
Base acrylate monomer or long chain hydrocarbon groups acrylate monomer polymerize the polyacrylate of acquisition, polymer poly after emulsifying altogether
Acrylate can include tool at least one of fluorohydrocarbon base acrylate monomer and long chain hydrocarbon groups acrylate monomer monomer knot
Structure unit, fluorine-containing alkyl or long chain hydrocarbon groups in polymer polyacrylate can assign polymer preferable waterproofness, can
To form microcosmic concaveconvex structure in substrate surface, waterproof performance and durable water resistant performance are further improved, and process and continue
Property is good.When above-mentioned hydrophobic nano-silica modified polyacrylate dispersion liquid is applied to textile, it may have preferable resistance to
Wash performance.
It should be noted that in the present embodiment, fluorine-containing alkyl acrylate monomer and long chain hydrocarbon groups acrylate monomer system
Referred to as monomer.Hydrophobic nano-silica and fluorine-containing alkyl acrylate monomer or long chain hydrocarbon groups acrylate monomer are through altogether
It polymerize in the polyacrylate of acquisition after emulsification, contains fluorine-containing alkyl acrylate monomeric units or long chain hydrocarbon groups propylene
Acid ester monomer unit.It can containing fluorine-containing alkyl acrylate monomeric units or long chain hydrocarbon groups acrylate monomeric units
The preferable waterproofness of polymer is assigned, allows polyacrylate to form microcosmic concaveconvex structure in substrate surface, further
Waterproof performance and durable water resistant performance are improved, and it is good to process duration.So that above-mentioned hydrophobic nano-silica is modified poly-
When acrylate dispersion liquid is applied to textile, it may have preferable washing fastness.
The molecular formula of the fluorine-containing alkyl acrylate monomer is CH in one of the embodiments,2=CR1COOR2,
Middle R1For H, Cl or C1~4Linear paraffin, R2For C4~16Fluorine-containing alkyl.For example, the fluorine-containing alkyl acrylate monomer packet
It includes but is not limited to: perfluorooctylethyl group methacrylate, perfluorooctylethyl group acrylate, perfluoro hexyl ethyl-methyl propylene
Acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro hexyl ethyl-ɑ-chloropropene acid esters (CH2=CClCOOCH2CH2C6F13)、
Perfluoro butyl ethylmethyl acrylate, perfluoro butyl ethyl propylene acid esters, perfluoro butyl ethyl-ɑ-chloropropene acid esters (CH2
=CClCOOCH2CH2C4F9).Preferably, the fluorine-containing alkyl acrylate monomer is perfluoro hexyl ethyl propylene acid esters.Such as
This, can make polyacrylate dispersion liquid play waterproof action preferably and process duration.
The long chain hydrocarbon groups acrylate monomer is CH in one of the embodiments,2=CR3COOR4It indicates, wherein R3
For H or C1~4Linear paraffin, R4For C12~30Alkyl.For example, C12~30Alkyl include but is not limited to dodecyl, the tetradecane
Base, cetyl, octadecyl, docosyl, laurylene base, octadecylene base, C12~30Naphthenic base etc. alkyl.For example,
The long chain hydrocarbon groups acrylate monomer includes but is not limited to: (methyl) dodecyl acrylate, (methyl) tetradecyl acrylate,
(methyl) Process Conditions of Cetane Acrylate, (methyl) octadecyl acrylate, (methyl) Behenyl acrylate etc..Preferably, the long-chain
Acrylate monomer is octadecyl acrylate.
One preferred embodiment is that the hydrophobic nano-silica modified polyacrylate dispersion liquid contains simultaneously
Fluorohydrocarbon base acrylate monomer and long chain hydrocarbon groups acrylate monomer, and the mass parts of fluorine-containing alkyl acrylate monomer are 80
Part, the mass parts of the long chain hydrocarbon groups acrylate monomer are 15 parts to 17 parts, and the fluorine-containing alkyl acrylate monomer is complete
Fluorine hexyl ethyl propylene acid esters, the long chain hydrocarbon groups acrylate monomer are octadecyl acrylate.In this way, being studied by applicant
It was found that having preferable processing duration and waterproof persistence.
It should be noted that the dosage of dewatering nano silica is subject to the performance for not influencing final products, one implements
In example, the quality dosage of dewatering nano silica is hydrophobic nano-silica modified polyacrylate dispersion liquid gross mass
20%.It so, it is possible so that there is hydrophobic nano-silica modified polyacrylate dispersion liquid preferable processing to continue
Property.
In the application, by using hydrophobic nano-silica, have with the polyacrylate that monomer generates preferable
Waterproofness being capable of preferably emulsion reaction and during enabling to hydrophobic nano-silica and monomer emulsion polymerization.
It should be noted that if using hydrophilic nano silica, be easy to leave following defect: hydrophilic nano silica is by shadow
The waterproof effect for ringing hybridized polymer, will be difficult in system of the invention newborn without the silica of hydrophilic, hydrophobic modification
Change, and does not have preferable waterproof effect.The polyacrylate of the application is by monomer and hydrophobic nano-silica through altogether
It polymerize after emulsification and obtains, preferable waterproof effect and processing duration can be played.
In one embodiment, the hydrophobic nano-silica passes through nano silicon dioxide sol and alkylsiloxane chemical combination
Object or alkyl siloxane polymer reaction are prepared, and the alkylsiloxane compound includes the siloxanes with hydrophobic grouping
Compound, the alkyl siloxane polymer include the siloxane polymer with hydrophobic grouping.For example, the alkylsiloxane
Compound includes the silicone compounds with hydrophobic grouping, and the alkyl siloxane polymer includes the silicon with hydrophobic grouping
Oxygen alkane polymer.For example, the silicone compounds containing hydrophobic grouping are at least to contain a C4Or more hydrophobic alkane
Base chain and silicone compounds at least containing an alkoxy base, for example, the silicone compound containing hydrophobic grouping
Object is selected from trimethoxy silane, isobutyl group trialkoxy silane, butyl trialkoxy silane, octyltrialkoxysilane, 12
At least one of alkyltrialkoxysilaneand, cetyl trialkoxy silane, octadecyltrialkoxysilane etc..Example
Such as, the siloxane polymer containing hydrophobic grouping selects methyl alkoxy silicone oil.Preferably, described containing hydrophobic grouping
Silicone compounds or siloxane polymer containing hydrophobic grouping are trimethoxysilane, octyl trimethoxy silane
One of with MethylethoxylsiliconFluid Fluid.For example, the alkylsiloxane compound or alkyl siloxane polymer include but not
It is limited to: methyl trialkoxysilane, ethyltrialkoxysilanes, propyl trialkoxy silane, isopropyl trialkoxy silane, two
Methyl dioxane oxysilane, diethyl dialkoxy silicane, dipropyl dialkoxy silicane, diisopropyl dialkoxy silicane
Deng.It so, it is possible preferably to prepare hydrophobic nano-silica.It should be noted that nano silicon dioxide sol is to receive
Dispersion liquid of the silica dioxide granule of meter level in water or in solvent.For example, nano silicon dioxide sol abbreviation silica solution.This reality
It applies the hydrophobic nano-silica in example and is referred to as hydrophobic nano-silica colloidal sol.
In order to reach preferable hydrophobically modified effect, in an embodiment, the nano silicon dioxide sol and alkyl silicon oxygen
The mass ratio of hydride compounds or alkyl siloxane polymer is that 5:1~15:1 is advisable.For example, the nano silicon dioxide sol with
The mass ratio of alkylsiloxane compound is 5:1~15:1.For example, the nano silicon dioxide sol polymerize with alkylsiloxane
The mass ratio of object is 5:1~15:1.It so, it is possible to reach preferable hydrophobically modified effect.
For example, the hydrophobic nano-silica is preferably advisable with colloidal state directly application, nano silicon dioxide sol institute
The dispersion solvent of use is usually one of propylene glycol methyl ether acetate (PMA), dipropylene glycol methyl ether acetate (DPMA).Institute
Stating nano silicon dioxide sol can be purchased from the market acquisition, the solvent produced such as Zhangjiagang Churen New Materials Technology Co., Ltd.
Type silica solution CR-23PMA；The nano silicon dioxide sol can also be synthesized using literature procedure, such as " plating and coating
Periodical " preparation method reported in the 6th phase " preparation and application of hydrophobically modified silica solution " of volume 35: to alcohol dispersing type silica solution
It is middle that a certain amount of hydrophobic modifier is added, carry out hydrophobically modified, PMA or DPMA be added after the reaction was completed, then steam alcohol to get
To target solvent type silica solution product.The above is only for example, but being not limited to the above method.
In one embodiment, surfactant is nonionic surfactant or the surfactant is by non-ionic surface
Activating agent compounds the mixed surfactant to be formed with cationic surfactant.Nonionic surfactant usually contains non-fluorine
The hydrophobic section of the hydrophilic section and alkyl of polyethers and/or polyhydroxy group, hydrophilic section and hydrophobic section strong, ehter bond, nitrogen-atoms by ester
Deng connection, polyether group is connected with polyhydroxy group by ehter bond.For example, nonionic surfactant includes but is not limited to: this
Disk (also known as sapn or this Pan) series (S-80, S-40, S-60 etc.), TWEEN Series (T-60, T-20 etc.), aliphatic alcohol polyethenoxy
Ether/polyethenoxy ether (AEO-5, AEO-9, AEO-15, isomery alcohol ether E-1306 etc.), aliphatic acid polyethenoxy/polyoxypropylene ester
(LAE-9, polyoxyethylene oleate A-105, SG-100 etc.), aliphatic amine polyoxyethylene ether (AC-1810, AC-1820 etc.).Sun from
Sub- surfactant usually contains the hydrophilic section of quaternary ammonium salt cationic group and the hydrophobic section of alkyl, for example, cationic surface is living
Property agent includes but is not limited to: hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, octacosyl dimethyl chloride
Change ammonium, Gemini quaternary ammonium salt etc..It should be noted that dosage of surfactant has certain limitations relative to polyacrylate, lead to
Often it is subject to not the waterproof performance for influencing product, preferred quality dosage is no more than the 15% of the quality of polyacrylate.It needs
Illustrate, the quality of polyacrylate, can be obtained according to the gross mass of monomer and hydrophobic nano-silica, e.g., is gathered
The quality of acrylate is the summation of the quality of monomer and hydrophobic nano-silica.When monomer further includes other monomers,
It is also required to count in the quality of other monomers, that is, the quality of polyacrylate is hydrophobic nano-silica, fluorine-containing alkyl third
The summation of olefin(e) acid ester monomer or the quality of long chain hydrocarbon groups acrylate monomer, other monomers.In the present embodiment, by adding
Enter surfactant, the combination interface of dispersion liquid and substrate can be improved, so that in conjunction with more uniformly, and adsorb relatively firm.
Hydrophobic nano-silica modified polyacrylate dispersion liquid further includes hydrotropy in one of the embodiments,
Agent, the mass parts of the cosolvent are 0.1 part to 15 parts, so, it is possible the subsequent use convenient for dispersion liquid.For example, cosolvent
Water-soluble solvent, for example, the cosolvent includes but is not limited to: acetone, methanol, ethyl alcohol, isopropanol, glycerol, propylene glycol, the third three
Alcohol, ethylene glycol, propylene glycol, butanediol, dipropylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, 5- decine -4,7- glycol -
2,4,7,9- tetramethyl, 3-Methoxy-3-methyl-1-butanol, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate etc..
Preferably, cosolvent includes at least one of propylene glycol methyl ether acetate (PMA) and dipropylene glycol methyl ether acetate (DPMA).
It so, it is possible to play preferable dissolution assistant effect to the polyacrylate that hydrophobic nano-silica and monomer reaction generate.
It is held to further increase hydrophobic nano-silica modified polyacrylate dispersion liquid waterproof performance and processing
Continuous property, in an embodiment, the hydrophobic nano-silica modified polyacrylate dispersion liquid further includes following mass parts
At least one of monomer:
3 parts of cross-linking monomer；
Other acrylate monomers (i.e. non-fluorine-containing alkyl acrylate monomer and the non-long chain hydrocarbons of non-foregoing acrylates type
Base acrylate monomer) 3 parts；
2 parts of non-crosslinked non-acrylate type unit containing double bond monomer；
It so, it is possible so that the polyacrylate that each monomer is reacted with hydrophobic nano-silica further includes crosslinking
Monomeric unit, other acrylate monomeric units of non-foregoing acrylates type and non-crosslinked non-acrylate type contain double bond monomer
At least one of unit, and then hydrophobic nano-silica modified polyacrylate dispersion liquid waterproof can be further increased
Performance and processing duration.
It should be noted that cross-linking monomer is usually the monomer containing two or more carbon-carbon double bond or contains carbon-carbon double bond
With the monomer of at least one non-double bond reaction active groups, group such as hydroxyl group, carboxylic group, epoxy with reactivity
Group, isocyanate groups or blocked isocyanate groups, amino group etc..In one embodiment, cross-linking monomer includes but unlimited
In: pentaerythrite list (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylic acid
Ester, pentaerythrite four (methyl) acrylate, (methyl) hydroxy-ethyl acrylate, 3- chlorine-2-hydroxyl-propyl (methyl) acrylic acid
Ester, allyl alcohol, allyl hydroxyl ethylether, N hydroxymethyl acrylamide, (methyl) glycidyl acrylate, allyl isocyanide
Acid esters, isocyanates ethyl acrylate, (methyl) acrylamide, methacrylic acid urea groups ester, Diacetone Acrylamide etc..Such as
This generates cross-linking monomer unit, for improving the binding strength of dispersion liquid and substrate by the way that cross-linking monomer is added in the polymer
There is certain influence, selects suitable cross-linking monomer that can further increase binding strength.Preferably, cross-linking monomer is preferably propylene
One of acid glycidyl ester or Diacetone Acrylamide.
In one embodiment, other acrylate monomers of non-foregoing acrylates type include but is not limited to: (methyl) propylene
Sour methyl esters, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid just oneself
Ester, 2-Ethylhexyl Methacrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid are different
Last of the ten Heavenly stems ester, (methyl) dodecyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, isobornyl acrylate etc..
In one embodiment, non-crosslinked non-acrylate type includes but is not limited to containing double bond monomer: styrene, methylbenzene second
Alkene, vinyl chloride, vinylidene chloride etc..
It further include chain-transferring agent in hydrophobic nano-silica modified polyacrylate dispersion liquid in one embodiment, with
Adjust the size of polymer molecular weight.For example, chain-transferring agent can be selected from alkyl thiol compound for example butanethiol, octyl mercaptan,
2 mercapto ethanol, lauryl mercaptan etc. or the inorganic salts such as sodium hypophosphite, sodium hydrogensulfite, it is preferred that chain-transferring agent is 12
Alkyl hydrosulfide.For example, dosage is the 0.1%~3% of monomer gross mass dosage when chain-transferring agent is lauryl mercaptan.
In one embodiment, pH adjusting agent can also be added into system before polymerization or after polymerization as needed, that is, hydrophobic
Further include pH adjusting agent in the nano-silicon dioxide modified polyacrylate dispersion liquid of property, pH adjusting agent include but is not limited to acetic acid,
Sodium acetate, ammonium acetate, hydrochloric acid, phosphoric acid, potassium dihydrogen phosphate, disodium hydrogen phosphate etc..For example, pH adjusting agent is acetic acid, mass parts
It is 0.5 part.
Above-mentioned hydrophobic nano-silica modified polyacrylate dispersion liquid, hydrophobic nano-silica and hydrofluorocarbons
Base acrylate monomer or long chain hydrocarbon groups acrylate monomer polymerize the polyacrylate of acquisition, polymer poly after emulsifying altogether
Acrylate can include tool at least one of fluorohydrocarbon base acrylate monomer and long chain hydrocarbon groups acrylate monomer monomer knot
Structure unit, fluorine-containing alkyl or long chain hydrocarbon groups in polymer polyacrylate can assign polymer preferable waterproofness, can
To form microcosmic concaveconvex structure in substrate surface, waterproof performance and durable water resistant performance are further improved, and process and continue
Property is good.When above-mentioned hydrophobic nano-silica modified polyacrylate dispersion liquid is applied to textile, it may have preferable resistance to
Wash performance.
The preparation method of the hydrophobic nano-silica modified polyacrylate dispersion liquid of the application can pass through lotion
Polymerization or solution copolymerization method obtain.Preferably, using emulsion polymerization.
In one embodiment, emulsion polymerization preparation process is as follows: in the presence of emulsifier, emulsifying monomer in water, so
It is warming up to 50 DEG C~95 DEG C of reaction temperature stirring polyase 13 hour~15 hour afterwards.Polymerization can using oil-soluble initiator or
Water soluble starter.Oil-soluble initiator includes but is not limited to the azodiisobutyronitrile of azo, the benzoyl peroxide first of peroxide
Acyl, di-tert-butyl peroxide etc..Water soluble starter includes but is not limited to potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azo
Diisobutyl ether hydrochloride, hydrogen peroxide, 3- carboxyl acrylic peroxide etc..Relative to the monomer of 100 mass parts, initiator is used
Amount is 0.05~5wt%.When selecting oil-soluble initiator, it is preferable that initiator is added in monomer and emulsifies again.It is elected
When with water soluble starter, it is preferable that after monomer emulsification, add initiator.In addition, when using water soluble starter,
And when containing cationic emulsifier in emulsifier, initiator preferred cationic type initiator or non-ionic initiator.
It is uniformly dispersed in order to obtain, the dispersion liquid that storage stability is good, in an embodiment, emulsifies a laggard stepping in monomer
Horizontal high voltage homogeneous, ultrasonication or height press through the processing such as film.The crushing energy that so, it is possible generation higher-strength, so that monomer
Droplet is further miniaturize, and stability enhances, and then can further increase polymer stabilisation.
In one embodiment, the preparation method of the hydrophobic nano-silica modified polyacrylate dispersion liquid includes such as
Lower step:
S110: being added reaction kettle for each component, is warming up to 40~45 DEG C of progress pre-emulsifications, obtains emulsion；
In the present embodiment, by the way that reaction kettle is added in each component, that is, by hydrophobic nano-silica, surfactant,
Water, monomer (fluorine-containing alkyl acrylate monomer and/or long chain hydrocarbon groups acrylate monomer) are added in reaction kettle, it is warming up to 40~
45 DEG C of progress pre-emulsifications, obtain emulsion；When contain cosolvent when, cosolvent should be also added, when in monomer contain other lists
When body, other monomers should be also added.
S120: by emulsion high-pressure homogeneous 30 minutes under the pressure of 400bar-500bar, homogenizing fluid is obtained；
S130: initiator being added into homogenizing fluid, after stirring and evenly mixing, is warming up to 70~75 DEG C of reaction 5h, that is, is prepared
The hydrophobic nano-silica modified polyacrylate dispersion liquid.
It so, it is possible preferably to prepare hydrophobic nano-silica modified polyacrylate dispersion liquid.It is prepared
Hydrophobic nano-silica modified polyacrylate dispersion liquid has preferable waterproof performance and durable water resistant performance, and processes
Duration is good.When above-mentioned hydrophobic nano-silica modified polyacrylate dispersion liquid is applied to textile, it may have preferably
Washing fastness.
Hydrophobic nano-silica modified polyacrylate dispersion liquid of the invention can be used alone, can also be with it
Its water-proofing treatment liquid is used cooperatively.Other water-proofing treatment liquid can be floride-free water-proofing treatment liquid and be also possible at fluorine-containing waterproof
Manage liquid, but should ensure that the treatment fluid that compound with dispersion liquid of the invention ionic upper holding always, otherwise possibility compositional liquor can
It can precipitate.
Hydrophobic nano-silica modified polyacrylate dispersion liquid of the invention can be acted on using common method
In in substrate processed.It is generally as follows: hydrophobic nano-silica modified polyacrylate dispersion liquid is diluted with water to obtain
Treatment fluid, then by the methods of dip coated, spraying coating treatment fluid to be attached in substrate, pricked using pressure and/or high
Warm drying process obtains water-proofing treatment substrate.It is crosslinked agent emulsion into blocked isocyanate in addition, can also compound in treatment fluid,
Pressure pricks and generates crosslinking after high-temperature process, further increases durable water-repellency.Other need can also be added according to product requirement
Want auxiliary agent.Composition can be usually diluted to 0.03%~3% mass concentration.It is also understood that the application hydrophobicity is received
The silica modified polyacrylate dispersion liquid of rice needs to be diluted to 0.03%~3% mass concentration.That is, hydrophobic nano two
The mass ratio of silica modified polyacrylate dispersion liquid and treatment fluid is 0.03%~3%.
The present invention is by adopting the above-described technical solution, have the advantages that
Hydrophobic nano-silica modified polyacrylate dispersion liquid good emulsion stability of the invention, lotion and
Processing duration is good, and processed textile water-proof performance and durable water resistant performance are excellent.
Continue to disperse hydrophobic nano-silica modified polyacrylate of the invention combined with specific embodiments below
Liquid is explained.
One, the preparation of hydrophobic nano-silica
Hydrophobic nano-silica A: it weighs 100g methanol silica solution (wherein silica solution 30g, methanol 70g) and pours into
In 250ml three-necked flask, it is slowly added to the trimethoxy silane of 10g under the conditions of 60 DEG C of stirring in water bath, isothermal reaction 1h, then plus
Enter 2g MethylethoxylsiliconFluid Fluid the reaction was continued 1h, 50g dipropylene glycol methyl ether acetate (DPMA) solvent is then added, is uniformly mixed
After be transferred on rotary evaporator, methanol is removed under reduced pressure, after continuously add DPMA to effective component be 30%.
Hydrophobic nano-silica B: it weighs 100g methanol silica solution (wherein silica solution 30g, methanol 70g) and pours into
In 250ml three-necked flask, be slowly added under the conditions of 60 DEG C of stirring in water bath 6g trimethoxysilane reaction 1h, then plus
Enter 50g propylene glycol methyl ether acetate (PMA) solvent, is transferred on rotary evaporator after mixing, methanol is removed under reduced pressure, it is subsequent
It is continuous be added PMA to effective component be 30%.
Hydrophobic nano-silica C: it weighs 100g methanol silica solution (wherein silica solution 30g, methanol 70g) and pours into
In 250ml three-necked flask, it is slowly added to the trimethoxy silane of 5g under the conditions of 60 DEG C of stirring in water bath, isothermal reaction 1h, then plus
Enter 3g octyl trimethoxy silane the reaction was continued 1h, 50g dipropylene glycol methyl ether acetate (DPMA) solvent is then added, mixing is equal
Be transferred on rotary evaporator after even, methanol be removed under reduced pressure, after continuously add DPMA to effective component be 30%.
Two, each specific embodiment and comparative example
The formula of each specific embodiment and the dispersion liquid of comparative example is shown in Table 1.
Raw material code name
Perfluoro hexyl ethyl propylene acid esters: C6
Octadecyl acrylate: SA
Glycidyl acrylate: GA
Diacetone Acrylamide: DAAM
Octadecyltrimethylammonium chloride: 1831
The process recipe table (being mass fraction in table) of each embodiment of table 1 and each comparative example
Note: above embodiments and comparative example are the theoretical solid content of 30wt%.The effective mass of hydrophily silica solution contains
Amount is 30%, and solvent is methanol.
Embodiment 1
By 100 mass parts C6, the hydrophobic nano-silica B of 50 mass parts, 2 mass parts S-60,3 mass parts AEO-9,
Reaction kettle is added in 2 mass parts AC-1810,3 mass parts 1831 and 253 mass parts water, is warming up to 40~45 DEG C of progress pre-emulsifications.So
High-pressure homogeneous 30 minutes afterwards, homogenizing fluid is transferred to reaction kettle, opens stirring.By 0.5 mass parts initiator azo diisobutyl
Amidine hydrochloride (AIBA), which dissolves in the water of 5 mass parts, forms homogeneous solution, and reaction kettle is added.Then heat to 70~75 DEG C of reactions
5h obtains hydrophobic nano-silica modified polyacrylate dispersion liquid of the invention.
Embodiment 2~3 and comparative example 1~3 use technique same as Example 1, and see Table 1 for details for specific formula.First will
Reaction kettle is added in ingredient other than initiator, is warming up to 40~45 DEG C of progress pre-emulsifications.It then high-pressure homogeneous 30 minutes, will
Homogenizing fluid is transferred to reaction kettle, opens stirring.Then by initiator water and AIBA be mixed to form after homogeneous solution be added it is anti-
Answer kettle.70~75 DEG C of reaction 5h are then heated to, the dispersion liquid of embodiment 2~3 and comparative example 1~3 is respectively obtained.
Embodiment 4
By the C6 of 80 mass parts, non-hydrophilic type silica solution A, the CA of 15 mass parts, the GA of 3 mass parts, 15 of 40 mass parts
The tripropylene glycol of mass parts, the S-60 of 2 mass parts, the AEO-9 of 3 mass parts, the AC-1810 of 2 mass parts, 3 mass parts 1831
And 238 mass parts water be added reaction kettle, be warming up to 40~45 DEG C of progress pre-emulsifications.Then high-pressure homogeneous 30 minutes, by homogeneous
Liquid is transferred to reaction kettle, opens stirring.The initiator A IBA of 0.5 mass parts is dissolved in the water of 5 mass parts and forms homogeneous solution,
Reaction kettle is added.It then heats to 65 DEG C of beginning clock reactions, and starts in reaction the vinyl chloride for being passed through 2 mass parts in rear 1h.
70~75 DEG C of continuation polymerization reaction 5h are warming up to, fluorine silicon hybridization polyacrylate dispersion liquid of the invention is obtained.
Comparative example 4 uses technique same as Example 4, and see Table 2 for details for specific formula.That is, will first remove initiator and chloroethene
Alkene with for ingredient be added reaction kettle, be warming up to 40~45 DEG C of progress pre-emulsifications.Then high-pressure homogeneous 30 minutes, homogenizing fluid is turned
Reaction kettle is moved to, stirring is opened.By in initiator water and AIBA be mixed to form after homogeneous solution and reaction kettle be added, then heat up
To 65 DEG C of beginning clock reactions, and start to be passed through vinyl chloride in rear 1h in reaction.70~75 DEG C of continuation polymerization reaction 5h are warming up to,
The dispersion liquid of comparative example 4.
Three, experiment test
The dispersion liquid of each embodiment and comparative example is diluted to 0.5% concentration, then to test fabric cloth at
Reason, then pressure bundle is carried out with press, 150 DEG C of temperature is heat-treated cloth 1 minute to get test sample is arrived later.Test method is such as
Under:
(1) waterproofing tests:
Waterproofing property evaluation standard is executed by GB/T 4745-1997 textile fabric surface moisture resistance measurement dip experiment, is detailed in
Table 2:
2 waterproofing property evaluation standard of table: GB/T 4745-1997 textile fabric surface moisture resistance measures dip experiment
| Waterproofing grade | State |
| 5 | Surface is without wet |
| 4 | Surface moistens on a small quantity |
| 3 | Surface portion is wet |
| 2 | Surface wettability |
| 1 | Surface is all wet |
(2) washing fastness is tested
It is washed by the decantation test method in GB 12799-91 oil resistant water resistant protective garment safety and sanitation performance requirement,
Then waterproofing tests are carried out again.
(3) duration performance testing is processed
The dispersion liquid that 1kg concentration is 0.5% is prepared, by Cloth Cutting to be processed at 20cm × 20cm size, according to sample
Preparation method first cloth is handled, later at after the same method successively to 2~n piece cloth
Reason.And every cloth waterproof performance is tested, by the processing duration of waterproof property evaluation dispersion liquid, (waterproofing grade is with 4-For boundary
Limit).When n-th cloth, waterproofing grade 4-；When (n+1)th cloth, waterproofing grade is not achieved 4-, then processing duration is
N piece.N is bigger, illustrates that processing duration is better.
Test result is as shown in table 3:
The test result of the dispersion liquid of each embodiment of table 3 and each comparative example treated test sample
Note: critical washing times n refers to that waterproofing grade when washing n times is 5-, waterproofing grade when washing n+1 times will
It is reduced to 5-Below.
From the above, it can be seen that the hydrophobic nano-silica modified polyacrylate of present embodiments disperses
Liquid, with preferable waterproof performance, and wash resistant number is higher, and processing duration is also preferable.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.It should be noted that " in an embodiment ", " example of the application
Such as ", " for another example ", it is intended to the application is illustrated, rather than for limiting the application.Embodiment described above only table
Several embodiments of the invention are reached, the description thereof is more specific and detailed, and but it cannot be understood as to patent of invention
The limitation of range.It should be pointed out that for those of ordinary skill in the art, in the premise for not departing from present inventive concept
Under, various modifications and improvements can be made, and these are all within the scope of protection of the present invention.Therefore, the protection of the invention patent
Range should be determined by the appended claims.
Claims (10)
1. a kind of hydrophobic nano-silica modified polyacrylate dispersion liquid, which is characterized in that including following mass parts
Each component:
40 parts to 66.7 parts of hydrophobic nano-silica；
10 parts to 15 parts of surfactant；
243 parts to 264 parts of water；
The hydrophobic nano-silica modified polyacrylate dispersion liquid further include in the monomer of following mass parts at least
It is a kind of:
80 parts to 100 parts of fluorine-containing alkyl acrylate monomer；
15 parts to 100 parts of long chain hydrocarbon groups acrylate monomer.
2. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 1, which is characterized in that institute
The molecular formula for stating fluorine-containing alkyl acrylate monomer is CH2=CR1COOR2, wherein R1For H, Cl or C1~4Linear paraffin, R2For
C4~16Fluorine-containing alkyl.
3. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 2, which is characterized in that institute
Stating fluorine-containing alkyl acrylate monomer is perfluoro hexyl ethyl propylene acid esters.
4. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 1, which is characterized in that institute
Stating long chain hydrocarbon groups acrylate monomer is CH2=CR3COOR4It indicates, wherein R3For H or C1~4Linear paraffin, R4For C12~30's
Alkyl.
5. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 4, which is characterized in that institute
Stating long chain hydrocarbon groups acrylate monomer is octadecyl acrylate.
6. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 1, which is characterized in that institute
The quality for stating dewatering nano silica is no more than the total matter of hydrophobic nano-silica modified polyacrylate dispersion liquid
The 20% of amount.
7. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 1, which is characterized in that institute
It states hydrophobic nano-silica and passes through nano silicon dioxide sol and alkylsiloxane compound or alkyl siloxane polymer
Reaction is prepared,
The alkylsiloxane compound includes the silicone compounds with hydrophobic grouping, the alkyl siloxane polymer packet
Containing the siloxane polymer with hydrophobic grouping.
8. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 7, which is characterized in that institute
It states the silicone compounds containing hydrophobic grouping and is selected from isobutyl group trialkoxy silane, butyl trialkoxy silane, three alkane of octyl
In oxysilane, dodecyl trialkoxy silane, cetyl trialkoxy silane and octadecyltrialkoxysilane
One kind, the siloxane polymer containing hydrophobic grouping are methyl alkoxy silicone oil.
9. hydrophobic nano-silica modified polyacrylate dispersion liquid according to claim 7, which is characterized in that institute
State the silicone compounds containing hydrophobic grouping or the siloxane polymer containing hydrophobic grouping be trimethoxysilane,
At least one of octyl trimethoxy silane and MethylethoxylsiliconFluid Fluid.
10. a kind of preparation method of hydrophobic nano-silica modified polyacrylate dispersion liquid as described in claim 1,
It is characterized by comprising the following steps:
Reaction kettle is added in each component, 40~45 DEG C of progress pre-emulsifications is warming up to, obtains emulsion；
By emulsion high-pressure homogeneous 30 minutes under the pressure of 400bar-500bar, homogenizing fluid is obtained；
Initiator is added into homogenizing fluid, after stirring and evenly mixing, is warming up to 70~75 DEG C of reaction 5h, that is, the hydrophobicity is prepared
Nano-silicon dioxide modified polyacrylate dispersion liquid.
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